EP0451736B1 - Elément photosensible développable en milieu aqueux - Google Patents

Elément photosensible développable en milieu aqueux Download PDF

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Publication number
EP0451736B1
EP0451736B1 EP91105460A EP91105460A EP0451736B1 EP 0451736 B1 EP0451736 B1 EP 0451736B1 EP 91105460 A EP91105460 A EP 91105460A EP 91105460 A EP91105460 A EP 91105460A EP 0451736 B1 EP0451736 B1 EP 0451736B1
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EP
European Patent Office
Prior art keywords
acid
elastomeric layer
labile
polymer
layer
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German (de)
English (en)
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EP0451736A2 (fr
EP0451736A3 (en
Inventor
Gwendyline Yuau Yu Teng Chen
Floyd A. Raymond
Jeffrey Jude Patricia
Walter Raymond Hertler
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EIDP Inc
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EI Du Pont de Nemours and Co
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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F3/00—Colour separation; Correction of tonal value
    • G03F3/10—Checking the colour or tonal value of separation negatives or positives
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists

Definitions

  • This invention relates to an aqueous processable photosensitive element for image reproduction. More particularly it relates to a photosensitive element comprising a photosolubilizable layer, an elastomeric layer, and a support.
  • the invention provides a photosensitive element adapted for the preparation of a colored image, the element comprising:
  • the invention provides a process for preparing a colored image comprising:
  • the transfer sheet may be removed, or it may be left in place to protect the image. Also, after step D the remaining regions of the photosolubilizable layer may be flooded with actinic radiation and removed by a washout step.
  • multiple colored images are prepared by steps (A) through (D). After removal of the removable support in step (G), the images are laminated in register to produce an image, having two or more colors, adhered to the transfer sheet. The temporary support is removed from the last colored image, and the last multicolor image is laminated to the receptor.
  • a four color surprint proof may be formed by selecting color transparencies and colorant material corresponding to yellow, magenta, cyan and black.
  • the invention provides a photosensitive element and a process adapted for the preparation of colored images.
  • the photosensitive element has a photosolubilizable layer consisting essentially of an acid-labile polymer and a photosolubilizing agent; an elastomeric layer; and a support.
  • the polymer backbone consists of the chain of atoms and/or moieties formed during polymerization.
  • the acid-labile group may be bound directly to the polymer backbone with no intervening atoms, such as in poly(THPMA), a homopolymer of tetrahydropropanyl methacrylate, and poly(THPA), a homopolymer of tetrahydropyranyl acrylate.
  • One or more additional atoms may be present between the acid-labile group and the polymer backbone.
  • An example of such indirect bonding is a polystyrene in which the acid-labile groups are attached to a phenyl substituent of the polymerized styrene.
  • the acid-labile polymer may be controlled by the choice of monomers and manner of polymerization.
  • the polymer may be either a homopolymer, a random or block copolymer, a terpolymer, or a higher polymer of various acid-labile monomers.
  • the copolymers and higher polymers may also contain conventional non-acid-labile monomers, such as methyl methacrylate, ethyl methacrylate, furfuryl methacrylate, benzyl methacrylate, and styrene. Small amounts (typically less than 5 mol%) of glycidyl methacrylate or similar monomers may be included to promote adhesion. However, monomers having groups that easily hydrolyze or thermally cleave generally will not be included.
  • the polymer backbone of this polymer consists essentially of recurring units of tetrahydropyranyl acrylate. Because this polymer has a low glass transition temperature (Tg), the photosolubilizable layer formed from this polymer will not crack when coated on a flexible support.
  • Tg glass transition temperature
  • Acid-labile polymers may be prepared by (1) polymerization of acid-labile monomers using conventional polymerization techniques or (2) derivatization of a preformed polymer, such as by acid catalyzed reaction of a polymer containing carboxylic acid and/or ester groups with vinyl ethers.
  • Acid-labile monomers may be prepared by conventional synthesis techniques. An example is acid catalyzed reaction of methacrylic acid with an alkyl vinyl ether, such as, ethyl vinyl ether or dihydropyran. These monomers may be polymerized by group transfer polymerization, such as that described in U.S. Patent 4,417,034; free radical polymerization; or other conventional polymerization techniques, such as anionic polymerization.
  • Group transfer polymerization produces highly reproducible, nearly monodisperse (polydispersity less than 1.75 for the polymerization of methacrylate monomers and somewhat higher for acrylate monomers) materials.
  • Group transfer polymerization is particularly adapted to polymerization of methacrylate and acrylate monomers. The molecular weight of the polymer is dependent on the ratio of monomer to initiator; polydispersity is predominantly dependent on the polymerization conditions. Methods for controlling polydispersity in group transfer polymerization are disclosed in I. B. Dicker et al., Polym. Prepr. , Am. Chem. Soc., Div. Polym. Chem., 1987, 28 (1), 106.
  • the photosolubilizing agent When activated by actinic radiation, the photosolubilizing agent furnishes acid that catalyzes decomposition of the acid-labile polymer.
  • the agent may do so directly, or may be a system containing a sensitizer that causes the agent to liberate acid when exposed.
  • Examples of compounds and mixtures that can be used for this purpose are diazonium, phosphonium, sulfonium and iodonium salts; halogen compounds; o -quinone diazide sulfochlorides; organometal/organohalogen combinations; benzoin and o -nitrobenzyl esters of strong acids, e.g. toluene sulfonic acid; and N-hydroxy amide and imide sulfonates disclosed in U.S. Patent 4,371,605.
  • Preferred photosolubilizing agents are diaryliodonium or triarylsulfonium salts, generally salts with complex metal halides ions such as tetrafluoroborate, hexafluoroantimonate, hexafluoroarsenate, and hexafluorophosphate.
  • a sensitizer may be desirable to add to the system to adjust the spectral sensitivity to the available wavelength of actinic radiation.
  • the need will depend on the requirements of the system and the specific photosensitive compound used.
  • iodonium and sulfonium salts only respond to wavelengths below 300 nm. These compounds may be sensitized to longer wavelengths using polycyclic aromatic hydrocarbons such as perylene, pyrene, and anthracene, and derivatives thereof.
  • the decomposition of diaryliodonium and triarylsulfonium salts has also been sensitized by bis-( p -N,N-dimethylaminobenzyliden)-acetone.
  • the use of dye in the photosolubilizing agent especially a dye whose absorption extends well into the visible region of the spectrum, may be undesirable since such dyes may affect the color of the resulting image.
  • Anthracene bound sulfonium salts with chain lengths of three to four atoms, are efficient photosolubilizing agents. These compounds, disclosed in M. G. Tilley, Ph.D. Thesis, North Dakota State University, Fargo, ND (1988) [ Diss. Abstr. Int. B , 49 , 3791 (1989); Chem. Abstr. , 111 , 39942u], are a preferred class of photosolubilizing agents.
  • the most preferred photosolubilizing agent is ATASS, i.e., sulfonium, [3-(9-anthracenyl)propyl]diphenyl-, hexafluoroantimonate[-1], a compound wherein the anthracene and sulfonium salt are bonded by a three carbon chain.
  • ATASS i.e., sulfonium, [3-(9-anthracenyl)propyl]diphenyl-, hexafluoroantimonate[-1]
  • the amount of photosolubilizing agent in the photosolubilizable layer should generally be as low as possible without unduly sacrificing sensitivity, and typically is in the range of approximately 0.1% to 5% by weight of the photosolubilizable layer. Less than about 0.1% generally leads to insensitive compositions, while weight percentages greater than about 5% produce compatibility and control problems. For most acid-labile polymers, it is preferred to use approximately 0.5 to 3% by weight photosolubilizing agent in the photosolubilizable layer.
  • the elastomeric layer is a tacky or slightly soft, deformable organic material.
  • suitable materials for the elastomeric layer should restrain diffusion from the photosolubilizable layer into the elastomeric layer. In addition, these materials should be nonmigratory into the photosolubilizable layer.
  • Polymers of butadiene or isoprene; random, teleblock and block copolymers of butadiene and isoprene copolymerized with styrene, and poly( alpha -olefins) in which the alpha -olefin contains from about five to about ten carbon atoms may be selected to advantage.
  • Poly( alpha -olefins), particularly poly(1-octene) are preferred. It will be apparent that the elastomeric layer must be transparent for applications in which the developed image is viewed through the layer.
  • the elastomeric layer is present on a support.
  • the support may be any material having the necessary stiffness and dimensional stability, proper adhesion to the elastomeric layer, and resistance to the solvent used for washout, i.e., water or dilute aqueous base.
  • the support is preferably smooth.
  • Exemplary materials useful as supports include: films, such as a polyethylene terephthalate of photographic grade, which may be subbed as described in Alles U.S. Patent 2,779,684; adhesive subbed opaque polyethylene terephthalate film base, such as Melinex® sold by ICI Americas, Wilmington, DE; and paper stock treated to make it resistant to aqueous solvents.
  • the photosolubilizable layer is prepared by mixing the ingredients in a suitable solvent, such as 2-butanone, usually in the weight ratio of about 10:90 (solids to solvent), coating, and evaporating the solvent. Coating should be uniform. A typical coating weight of about 40 mg/dm 2 produces a dry thickness of about 0.004 mm.
  • a suitable solvent such as 2-butanone
  • the photosensitive element is prepared using conventional coating techniques.
  • the elastomeric layer may be coated onto the support. After the solvent has evaporated, the photosolubilizable layer is coated over the elastomeric layer.
  • a release film such as a polyethylene coversheet may be used to protect the photosolubilizable layer until the element is used.
  • the photosolubilizable layer may coated onto a coversheet.
  • a release film such as polyethylene, optionally may be placed over the coating to protect the photosolubilizable layer until the rest of the element is formed.
  • the elastomeric layer is coated over the photosolubilizable layer. If a release film is present on the photosolubilizable layer, it is stripped off before the elastomeric layer is coated. After the solvent has evaporated, the support is laminated to the surface of the elastomeric layer. The solvent for the elastomeric layer should not solubilize or have a deleterious effect on photosolubilizable layer.
  • the element may also be prepared using conventional multilayer coating techniques.
  • the photosolubilizable layer and the elastomeric layer may be coated simultaneously onto a coversheet, and the support laminated to the elastomeric layer.
  • the photosolubilizable layer and the elastomeric layer may be coated simultaneously onto the support, and, optionally, a coversheet laminated to the photosolubilizable layer.
  • actinic radiation is radiation which is active to produce the acid which catalyzes decomposition of the acid-labile polymer.
  • the radiation can be natural or artificial, monochromatic or polychromatic, incoherent or coherent. Most of the actinic radiation should be absorbed by the photosolubilizing agent for efficient image formation.
  • the temperature of the washout solvent should not greatly exceed room temperature since deformation of the elastomeric layer may occur at higher temperatures.
  • the exposed element may be gently brushed or rubbed with cotton.
  • the exposed and washed-out element may be allowed to air dry or dried with forced air.
  • Patent 3,060,024 ; transfer (Burg et al., U.S. Patent 3,060,025); hand-operated machine toning (Sandner, U.S. Patent 4,019,821); and automatic toning (Tobias, U.S. Patent 4,069,791).
  • the processed element may be used without further treatment if a single color surprint proof is desired.
  • the final image will consist of the exposed and washed-out photosolubilizable layer, toned elastomeric layer, and support.
  • a releasable support is not required for this application. However, if transfer to another substrate is desired, a releasable support, such as silicon treated polyethylene terephthalate film, must be used.
  • the image may be transferred using a transfer element comprising a transfer sheet and an elastomeric layer.
  • a transfer element comprising a transfer sheet and an elastomeric layer.
  • the materials which may used as the support may also be used as the transfer sheet.
  • the materials used for the elastomeric layer of the photosensitive element also may be used for the elastomeric layer of the transfer element.
  • the support may be removed and the image laminated to a receptor to form a surprint proof.
  • the receptor should be flat and, preferably, smooth. Typical receptors are the various types of paper used in printing.
  • the transfer sheet may be removed, or it may be left in place to protect the final image. If the transfer sheet is to be left in place, a transparent transfer sheet must be used.
  • a second colored image may laminated in register to the back of the toned elastomeric layer of the element consisting of: transfer sheet, elastomeric layer, exposed and washed-out photosolubilizable layer (unless it has been removed after the photosensitive element was formed), and toned elastomeric layer.
  • the image thus formed may be laminated to a receptor to produce a two color image.
  • additional colored images may be laminated in register to this image before final lamination to a the receptor.
  • a four-color surprint proof consisting of yellow, cyan, magenta, and black images, may be formed in this manner.
  • This example illustrates the preparation of a homopolymer of THPA by group transfer polymerization.
  • the preparation of THPA is described in J. E. Kearns, C. D. McLean, and D. H. Solomon, J. Macromol. Sci.-Chem. , A8 (4), 673-685, 1974.
  • This example illustrates the preparation of a homopolymer of THPA by group transfer polymerization.
  • This example illustrates the preparation of a poly(THPA) with a broad molecular weight distribution by free radical polymerization.
  • This example illustrates the preparation of 1-(ethoxy)-propyl methacrylate (EPMA) and its conversion to a homopolymer by free radical polymerization.
  • EPMA 1-(ethoxy)-propyl methacrylate
  • the reaction mixture was cooled to about 50°C, stirred at 50-54°C for 18 hr, and was then treated with 10 g of sodium bicarbonate and 40 g of anhydrous sodium sulfate. After filtration to remove the solids, the product was distilled three times from calcium hydride, phenothiazine, and diphenylpicrylhydrazyl to give 71.7 g of EPMA, bp 34-38.9°C (2.1-2.6 mm Hg). Calcd for C 9 H 16 O 3 : C, 62.77; H, 9.36. Found: C, 63.12; H, 9.11.
  • This example illustrates the preparation IEMA and its conversion to a homopolymer by free radical polymerization.
  • This example illustrates the preparation of a 40:60 (mol%) copolymer of THPMA and EPMA by free radical polymerization.
  • This example illustrates the preparation of a (61:39 mol%) block copolymer of THPMA and ethyl acrylate by group transfer polymerization.
  • This example illustrates the preparation of a (59:41 mol%) copolymer of THPMA and THPA by free radical polymerization.
  • the polymer was precipitated in methanol at -78°C in a blender to give, after drying at 0.1 mm for 24 hr, 24 g of poly(THPMA/THPA). NMR showed the polymer to be 59 mol% THPMA and 41 mol% THPA.
  • GPC M n 58,900; M w 126,100; M w /M n 2.15.
  • DSC T g 74°C with a decomposition endotherm at 160°C.
  • THPMA and furfuryl methacrylate were separately purified by passage over columns of basic alumina under argon. Following the procedure of example 4, to a solution of 0.74 mL (2.3 mmol) of TTEB and 0.15 mL of tetrabutylammonium biacetate (0.04 M in THF) in 75 mL of THF was added dropwise a mixture of 24 mL (24.6 g, 0.1445 mol) of THPMA and 22.2 mL (24 g, 0.1445 mol) of furfuryl methacrylate. NMR analysis of the reaction mixture showed residual monomers to be present.
  • Example 11 The procedure of Example 11 was repeated with the exception that the photosolubilizing agent consisted of Cyracure® UV6974 (1.0% in the coating solution for the photosolubilizable layer) and 9-anthracenemethyl butyrate (0.5% in the coating solution) and that the homopolymer of THPA described in Example 2 was used in the photosolubilizable layer in place of the polymer described in Example 1. Wash out time was 20 sec. Image quality as a function of exposure time is given in the following table. Exposure Time (sec) Image Quality (Dots Held) 7.5 2-99.5% 15 0.5-99% 20 0.5-98% 22.5 0.5-98% 30 0.5-98%
  • the photosolubilizable layer contained the homopolymer of THPA prepared in Example 3 (about 95%) and ATASS (about 5%).
  • the elastomeric layer was prepared by coating a solution prepared by mixing 10 gm of a 3% solution of a Krayton® D1107 in dichloromethane, 10 gm of a 3% solution of Diene 55AC in dichloromethane, 0.10 gm of poly(methyl 2-methylpentadienoate), 0.05 gm of 3M 2-ply tape (3M, St. Paul, MN), and 10 gm of dichloromethane using a a doctor knife with 3 mil gap. Exposure for 3.5 sec, washout for 25 sec in 0.4 N sodium hydroxide, and toning gave an image with 1-98% dots.
  • Example 11 Following the general procedure of Example 11 a photosensitive element was prepared and imaged.
  • the photosolubilizable layer was coated directly onto the elastomeric layer from a solution containing 10% of poly(EPMA) described in Example 5, 1% of Cyracure® UV6974, 0.4% of benzophenone, and 0.1% of 2-chlorothioxanthen-9-one in 2-butanone.
  • the elastomeric layer was a mixture Gentro® 1506 (about 22%) and Diene 55AC (about 78%). Exposure for 360 sec, washout for 180 sec in 0.4 N sodium hydroxide, and toning gave an image with 0.5-99.5% dots.
  • Example 11 Following the general procedure of Example 11 a photosensitive element was prepared and imaged.
  • the photosolubilizable layer was coated directly onto the elastomeric layer from a solution containing 10% of poly(IEMA) described in Example 6 and 0.5% of ATASS dissolved in 2-butanone (89%) and propylene carbonate (0.5%).
  • the elastomeric layer was poly(1-octene). Exposure for 10 sec, washout for about 30 sec in room temperature 0.4 N sodium hydroxide, and toning gave an image with 20-98% dots.
  • Example 11 Following the general procedure of Example 11 a photosensitive element was prepared and imaged.
  • the photosolubilizable layer was coated directly onto the elastomeric layer from a solution containing 10% of the copolymer of THPMA and EPMA described in Example 7 and 0.5% of ATASS dissolved in 2-butanone (89%) and propylene carbonate (0.5%).
  • the elastomeric layer was the same as used in Example 16. Exposure for 10 sec, washout for about 120 sec in hot tap water, and toning gave an image with 0.5-98% dots.
  • Example 11 Following the general procedure of Example 11 a photosensitive element was prepared and imaged.
  • the elastomeric layer was coated onto Melinex® from a solution containing 3% Gentro® 1506 in dichloromethane using a coating knife with a three mil gap.
  • the photosolubilizable layer was coated directly onto the elastomeric layer from a solution containing 10% of the block copolymer of THPMA and ethyl acrylate described in Example 8, 1% of Cyracure® UV6974, 0.4% of benzophenone, and 0.1% of 2-chlorothioxanthen-9-one in 2-butanone.
  • Exposure time was 120 sec.
  • the image was washed-out with room temperature 0.4 N sodium hydroxide. Washout time was about 180 sec. After toning, an image with 0.5% to 98% dots was obtained.
  • Example 11 Following the general procedure of Example 11 a photosensitive element was prepared and imaged.
  • the photosolubilizable layer was coated directly onto the elastomeric layer from a solution containing 10% of the copolymer of THPMA and THPA described in Example 9 and 0.5% of ATASS dissolved in 2-butanone.
  • the elastomeric layer was poly(1-octene). Exposure for 40 sec, washout for about 60 sec in tap water at 25°C, and toning gave an image with 0.5-80% dots.
  • Example 11 Following the general procedure of Example 11 a photosensitive element was prepared and imaged.
  • the photosolubilizable layer was coated directly onto the elastomeric layer from a solution containing 10% of the copolymer of THPMA and furfuryl methacrylate described in Example 10, 1% of Cyracure® UV6974, 0.4% of benzophenone, and 0.1% of 2-chlorothioxanthen-9-one in 2-butanone.
  • the elastomeric layer was a mixture Gentro® 1506 (about 22%) and Diene 55AC (about 78%). Exposure for 480 sec, washout for 180 sec in 0.4 N sodium hydroxide, and toning gave an image with 0.5-99.5% dots.
  • This example illustrates the preparation of a four color proof using a photosensitive element of this invention.
  • Step 1 Elastomeric Layer A solution of poly(1-octene) (2.0%) and Diene 55AC (1.0%) dissolved in toluene was coated onto a silicone treated polyethylene terephthalate support using a doctor knife with a 3 mil (75 micron) gap. The coating was allowed to air dry to produce an element consisting of: polyethylene terephthalate support and elastomeric layer.
  • Step 2 Photosensitive Element A solution of the homopolymer of THPA prepared in Example 2 (10%) and ATASS (0.126%) in 2-butanone was coated onto the elastomeric layer of the element formed in step 1 using a doctor knife with a 1 mil (25 micron) gap. The coating was allowed to air dry to produce a photosensitive element consisting of: polyethylene terephthalate support; elastomeric layer; and photosolubilizable layer.
  • Step 4 Washout and Toning The exposed sample was allowed to stand at room temperature for about 2-3 min. Then it was washed-out with room temperature tap water for 20 sec, dried, and toned with yellow toner as described in Step 4 of Example 11 to produce a yellow toned image consisting of: exposed and washed-out photosolubilizable layer; toned elastomeric layer; and support.
  • Step 6 Transfer Element
  • the coating solution for the elastomeric layer was coated onto polyethylene terephthalate film as described in Step 1 to produce a transfer element consisting of: polyethylene terephthalate transfer sheet and elastomeric layer.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Materials For Photolithography (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Claims (24)

  1. Un élément photosensible adapté à la préparation d'une image en couleurs, ledit élément comprenant :
    (1) une couche photosolubilisable consistant essentiellement en:
    (a) un agent photosolubilisant et
    (b) un polymère labile aux acides renfermant un squelette polymère et des groupes pendants labiles aux acides liés au squelette du polymère, lesdits groupes pendants labiles aux acides étant liés au squelette du polymère, lesdits groupes pendants labiles aux acides étant représentés par la formule :

            -CO 2 -C(R 1 )(OR 2 )-CH(R 3 )(R 4 )

    dans laquelle :
    R1 est un hydrogène ou un radical alkyle renfermant d'environ 1 à environ 6 atomes de carbone;
    R2 est un radical alkyle renfermant de 1 à environ 8 atomes de carbone;
    R3 et R4 sont chacun indépendamment un atome d'hydrogène ou un radical alkyle renfermant d'environ 1 à environ 6 atomes de carbone;
    où soit R1 et R2; R1 et R3; ou R2 et R3 peuvent être réunis pour former un cycle à 5-, 6- ,ou 7- éléments;
    (2) une couche élastomère, et
    (3) un support.
  2. L'élément selon la revendication 1 dans lequel ledit polymère renferme au moins approximativement 50% en moles de motifs répétitifs d'un ou de plusieurs monomères labiles aux acides.
  3. L'élément selon la revendication 2 dans lequel ledit monomère labile aux acides est un monomère acrylique, un monomère méthacrylique, ou un de leurs mélanges.
  4. L'élément selon la revendication 3 dans lequel ledit ledit groupe labile aux acides porte les substituants suivants: R1 et R4 représentent un atome d'hydrogène R2 est un groupe alkyle renfermant de 1 à 4 atomes de carbone; et R3 est un hydrogène ou CH3.
  5. L'élément selon la revendication 3 dans lequel ledit groupe labile aux acides porte les substituants suivants: R1 et R4 représentant un atome d'hydrogène; et R2 et R3 sont réunis pour former un cycle à 6 éléments.
  6. L'élément selon la revendication 3 dans lequel ledit polymère contient également au moins un monomère choisi dans le groupe constitué par : acrylate de méthyle, méthacrylate de méthyle, acrylate d'éthyle, méthacrylate d'éthyle, acrylate de furfuryle et méthacrylate de furfuryle.
  7. L'élément selon la revendication 1 dans lequel ledit polymère est essentiellement constitué de motifs récurrents d'un ou de plusieurs monomères labiles aux acides.
  8. L'élément selon la revendication 7 dans lequel ledit monomère labile aux acides est un monomère acrylique, un monomère méthacrylique, ou un de leurs mélanges.
  9. L'élément selon la revendication 7 dans lequel le monomère est un monomère acrylique dans lequel ledit groupe labile aux acides porte les substituants suivants : R1 et R4 sont des atomes d'hydrogène; R2 est un groupe alkyle renfermant de 1 à 4 atomes de carbone; et R3 est un hydrogène ou CH3.
  10. L'élément selon la revendication 7 dans lequel ledit polymère est choisi dans le groupe constitué par : poly(tétrahydropyranyle acrylate), poly[1-(éthoxy)-propyle méthacrylate], et copolymères de tétrahydropyranyle méthacrylate et tétrahydropyranyle acrylate.
  11. L'élément selon la revendication 1 dans lequel ledit agent photosolubilisant est un diaryliodonium, triarylsulfonium ou un sel de sulfonium lié à l'anthracène.
  12. L'élément selon la revendication 1 dans lequel ladite couche élastomère est un polymère de butadiène , d'isoprène ou d'une alpha-oléfine.
  13. L'élément selon la revendication 12 dans lequel ladite couche élastomère est une poly(alpha-oléfine) .
  14. L'élément selon la revendication 1 dans lequel ledit support est éliminable de la couche élastomère.
  15. Un procédé de préparation d'une image colorée comprenant, les étapes suivantes :
    (A) formation d'un élément photosensible multicouche comprenant, dans l'ordre :
    (1) une couche photosolubilisable consistant essentiellement en:
    (a) un agent photosolubilisant et
    (b) un polymère labile aux acides renfermant un squelette polymère et des groupes pendants labiles aux acides liés au squelette du polymère, lesdits groupes pendants labiles aux acides étant liés au squelette du polymère, lesdits groupes pendants labiles aux acides étant représentés par la formule :

            -CO 2 -C(R 1 )(OR 2 )-CH(R 3 )(R 4 )

    dans laquelle:
    R1 est un hydrogène ou un radical alkyle renfermant d'environ 1 à environ 6 atomes de carbone;
    R2 est un radical alkyle renfermant de 1 à environ 8 atomes de carbone;
    R3 et R4 sont chacun indépendamment un atome d'hydrogène ou un radical alkyle renfermant d'environ 1 à environ 6 atomes de carbone;
    où soit R1 et R2; et R3; ou R2 et R3 peuvent être réunis pour former un cycle à 5- , 6-,ou 7- éléments;
    (2) une couche élastomère, et
    (3) un support amovible.
    (B) formation d'une image latente dans ledit élément photosensible par exposition de ladite couche photosolubilisable à une radiation actinique à travers un transparent porteur de l'image;
    (C) élimination des zones de ladite couche photosolubilisable décomposées dans l'étape (B) par lavage avec une solution aqueuse, révélant ainsi des zones de la couche élastomère;
    (D) production d'une image colorée par application d'une matière colorante à la surface dudit élément photosensible, ladite matière colorante n'adhérant sélectivement que sur les zones révélées de la couche élastomère;
    (E) création d'un élément de transfert comprenant une feuille de transfert et une couche élastomère;
    (F) stratification de la surface de l'élément photosensible porteur de l'image colorée sur la couche élastomère du dit élément de transfert;
    (G) enlèvement du dit support amovible du dit élément photosensible pour révéler la couche élastomère; et
    (H) stratification de la couche élastomère du dit élément photosensible sur un récepteur.
  16. Le procédé selon la revendication 15 comprenant, entre les étapes D et E, l'étape d'exposition de l'ensemble du dit élément à une radiation actinique, et l'élimination du reste de la couche photosolubilisable par un solvant aqueux.
  17. Le procédé selon la revendication 15 dans lequel ledit polymère comprend au moins 50 moles % de motifs récurrents d'au moins un monomère labile aux acides.
  18. Le procédé selon la revendication 15 dans lequel ledit polymère est essentiellement constitué de motifs récurrents d'un ou de plusieurs monomères labiles aux acides.
  19. Le procédé selon la revendication 15 dans lequel ledit polymère est essentiellement constitué de motifs récurrents d'un ou de plusieurs monomères acryliques ou méthacryliques.
  20. Le procédé selon la revendication 15 dans lequel le monomère est un monomère acrylique dans lequel ledit groupe labile aux acides porte les substituants suivants: R1 et R4 sont des atomes d'hydrogène; R2 est un groupe alkyle renfermant de 1 à 4 atomes de carbone; et R3 est un hydrogène ou CH3.
  21. Le procédé selon la revendication 15 dans lequel ledit polymère est choisi dans le groupe constitué par : poly(tétrahydropyranyl acrylate), poly(1-(éthoxy)-propyl méthacrylate), et copolymères de tétrahydropyranyl méthacrylate et tétrahydropyranyl acrylate.
  22. Le procédé selon la revendication 15 dans lequel ledit solvant aqueux est l'eau.
  23. Le procédé selon la revendication 15 ou 16 dans lequel les étapes A à D sont réitérées pour produire au moins deux éléments photosensibles porteurs d'images colorées, et les éléments photosensibles sont superposés en correspondance les uns avec les autres.
  24. Le procédé selon la revendication 23 dans lequel quatre éléments photosensibles sont stratifiés en correspondance les uns avec les autres pour produire une épreuve en surimpression en quadrichromie.
EP91105460A 1990-04-10 1991-04-06 Elément photosensible développable en milieu aqueux Expired - Lifetime EP0451736B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US507339 1990-04-10
US07/507,339 US5071731A (en) 1990-04-10 1990-04-10 Aqueous processable photosensitive element with an elastomeric layer

Publications (3)

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EP0451736A2 EP0451736A2 (fr) 1991-10-16
EP0451736A3 EP0451736A3 (en) 1992-03-04
EP0451736B1 true EP0451736B1 (fr) 1997-07-09

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EP (1) EP0451736B1 (fr)
JP (1) JP2575237B2 (fr)
KR (1) KR910018848A (fr)
CN (1) CN1055609A (fr)
AU (1) AU627115B2 (fr)
CA (1) CA2038177A1 (fr)
DE (1) DE69126729T2 (fr)
SG (1) SG48136A1 (fr)

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US5219711A (en) * 1990-04-10 1993-06-15 E. I. Du Pont De Nemours And Company Positive image formation utilizing resist material with carbazole diazonium salt acid generator
US5262281A (en) * 1990-04-10 1993-11-16 E. I. Du Pont De Nemours And Company Resist material for use in thick film resists
US5206317A (en) * 1990-04-10 1993-04-27 E. I. Du Pont De Nemours And Company Resist material and process for use
US5212047A (en) * 1990-04-10 1993-05-18 E. I. Du Pont De Nemours And Company Resist material and process for use
US5225316A (en) * 1990-11-26 1993-07-06 Minnesota Mining And Manufacturing Company An imagable article comprising a photosensitive composition comprising a polymer having acid labile pendant groups
CA2138759A1 (fr) * 1992-07-31 1994-02-17 Allan Cairncross Methode et produit servant a monter des particules
DE4328676A1 (de) * 1993-08-26 1995-03-02 Hoechst Ag Lichtempfindliches Material und Verfahren zur Herstellung eines farbigen Bilds
EP0655653B1 (fr) * 1993-11-02 1999-05-19 Konica Corporation Méthode pour la formation d'une image colorée
US5597677A (en) * 1994-11-02 1997-01-28 Minnesota Mining And Manufacturing Company Photoimageable elements
US5563023A (en) * 1994-11-02 1996-10-08 Minnesota Mining And Manufacturing Co. Photoimageable elements
US5965321A (en) * 1997-09-25 1999-10-12 E. U. Du Pont De Nemours And Company Peel-apart photosensitive elements and their process of use
US6001532A (en) * 1997-09-25 1999-12-14 E.I. Dupont De Nemours And Company Peel-apart photosensitive elements and their process of use
US6884562B1 (en) * 1998-10-27 2005-04-26 E. I. Du Pont De Nemours And Company Photoresists and processes for microlithography
EP1240552B1 (fr) * 1999-08-13 2012-09-19 Intellectual Ventures Holding 40 LLC Compositions de photorésine développables dans l'eau
US6100006A (en) * 1999-08-19 2000-08-08 E. I. Du Pont De Nemours And Company Peel-apart photosensitive elements and their process of use
FR2809829B1 (fr) * 2000-06-05 2002-07-26 Rhodia Chimie Sa Nouvelle composition photosensible pour la fabrication de photoresist
JP2007246418A (ja) * 2006-03-14 2007-09-27 Canon Inc 感光性シランカップリング剤、パターン形成方法およびデバイスの製造方法
JP5965855B2 (ja) 2012-07-27 2016-08-10 富士フイルム株式会社 感活性光線性又は感放射線性樹脂組成物、それを用いたレジスト膜、パターン形成方法、及び電子デバイスの製造方法、並びに樹脂

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Publication number Publication date
SG48136A1 (en) 1998-04-17
KR910018848A (ko) 1991-11-30
JP2575237B2 (ja) 1997-01-22
EP0451736A2 (fr) 1991-10-16
US5071731A (en) 1991-12-10
AU627115B2 (en) 1992-08-13
CA2038177A1 (fr) 1991-10-11
CN1055609A (zh) 1991-10-23
DE69126729T2 (de) 1997-10-23
JPH04358154A (ja) 1992-12-11
DE69126729D1 (de) 1997-08-14
AU7420491A (en) 1991-11-07
EP0451736A3 (en) 1992-03-04

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